Disazo-dyestuffs insoluble in water and fiber dyed therewith



.5 invention, but they Patented Oct. 26, 1937 UNITED STATES DISAZO-DYESTUFFS INSOLUBLE i'NwArER- AND FIBER DYED THEREWITH Paul Jcrg; FrankIort-on-the-Main Hochst. Ge'ri many, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware N0 Drawing-V pplication May 1, 1937, ScrialNB- 140,269. In Germany A il 25, 193 I 7 8 claims. The present invention relates to ,disazo-dyestufis insoluble in water and to fiber dyed therewith; more particularly. it relates to compounds of the following-general formula:

wherein R stands for a radical of the benzene or naphthalene series. f

I have found that valuable disazo-dyestuifs insoluble in water are obtainable by diazotizing a 4-amino-2,5-dihydroxyalkoxy-2',6-dichloro 4"- nitro-1,1-azobenzene and combining it with an" arylide of 2-hydroxynaphthalene-B-carboxylic acid. The aminoazpo-compounds may be obtained by coupling 1 diazotized' 1-a'min0- 2,6-dichlorli i-nitrobenzene with aminohydroquinonedihydroxyalkyl ethers. H The new dyestuffs. when produced in substance, are valuable navy-blue to black pigments.j They are'also especially suitable :to'r the manufacture of water-insoluble dyestuifs on the fiber, by the ice-color method or by o ne of the known printing processes, for instance,

by the direct printing method. 0

rinsed againancl then rinsed; soapea Yatj boilinlg Qzempeiamre;

1 i contem la- 0 CHI-CHLOE are made into a. paste with 5 cc. of formic acid 6220 of 90 per cent. strength and stirred together with a 3.2 cc. of sulfuric acid of 36 B. A solution of 0.8 gram of sodium nitrite is run into thismixa ture while cooling with ice. After about 20 mini 'utes the "dlaz otizatiorf is "mashed: The b'a'th'fis v.125

made up to'l liter and neutralized withf i granis of good fastness to light are obtained."

Thedyestufi has the following forumla:

The navy-blue to black dyestuffs thus obtained are distinguished by their good properties of;

fastness. They surpass with respect to fastness ...to; ;light the known 'blackdyestufis obtainable from diazotized amino-azo-compounds and aryl- -;ides-of;2,3-hydroxynaphthoic acid, for instance, by the processes of German BatentsNos. 293,375,

'383,903,-391,091 and 392,077. They, therefore,

constitute a valuableadvance in the art.

The following examples serve to illustrate the are not intended to limit it thereto:

For producing the dyeings grams of cotton yarn are grounded in the grounding liquor for half-an-hour; squeezed and developed for half- 155 an-hour in the diazo-solution. The material is (2) Diazo-printmgcolor:'8() grams of dry diazo-salt containing 20 per cent by weightpf the .base of the followingjormula: 1

in the form of the zinc chloride double salt of the diazonium chloride, are stirred with water ,with' addition of 90 cc. of acetic acid of 50 pen- 50 .cent. strength and 400 grams of wheat starchtragacanth thickening are added. The whole is made up to '1 kilo.

Grounding liquor:--17

droxynaphthoylamino) 2-- methyl: 4 chloroben 7 oda'soluti nttg otcrystalized sodium acetater Blue- -black tints 7 zene, 20 grams of Monopol brilliant oil, 18 cc. components, for instance, 4-amino-2,5-di-betaof caustic soda solution of 38 Be; are dissolved with water and made up to 1 liter in the usual manner.

Printing prescriptiom-The dye goods are padded with'theegrounding liquor dried, printed V with the V diazorfiiiritingecolor; (m g; jagailiftan'd then treated with hot, dilute sodium carbonate solution. The material is then rinsed, soaped at boiling temperature, rinsed again and dried.

Navy-blue prints of good fastnes ig ht are obtained.

(3) 43.1 grams of the amino-azo body.oithe. formula: I

31 $CH2.CH2.0H are diazotized in the usual. manner: with dilute sulfuric acid and sodium nitr' The clear diazosolution which has been fi lte h suction is run into a sqlutiomrendered. alkaline with caus tic soda, of 35.8 grams of ".3 f.-Tliydro;xy'- naphthoylamino),.- 3 chloro.-. methoxybenzene,' and which contains.sucl'ij a quantity of; caustic soda solution sasis necessary to maintairr a caustic fal kaline reaction until the. coupling operation is fi Wa e-il sfepu in l l m iefi s.-.-'fi ished, the dyestuff obtaihedjisffilteredwitli tion and washed ngir eutrm. the dry'stat'e it is a blue blackpowderof good' fas'tness to light. By using other arylides of '2-h'yarexynapmha lene-3-carboxylic acid, dyestuffs of similar properties are obtained. The following table indihydroxy-propyloxy-ZZG dichloro 4'- nitro 1,1- azobenzene or 4-amino-2,5-di-gamma-hydroxybutyloxy-2',6-dichloro-4-nitro -1,1'- azobenzene.

Since an object of the present invention is to provide dyestuffs of good fastness properties which dyes'tufis are insoluble in water and alkalies, it isto be understood that the aromatic nuclei of the general formula appearing in the appended claims do not contain any substituents which are "lz ruiiwr to -render organic compounds soluble in water'br alkalies and to tend to depreciate the fastness of the dyestufis to alkalies. Substituents -,of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

. I claim: a

I i 1. The water-insoluble disazo-dyestufis of the following general formula:

I (laIkyLOlEI C1 O.alky1.0H OH- HCONHR oon omon being a blue-black powder I and yielding. when produced on the fiber, blue-black dyeings of good Diem-component" Qouplirig-coniponent' -Tint i 1-(2,3-hydroxynaphthoylamino)- (1.) 4-amino-2,5-di-beta-hydrcry#etlioxy i niethoxybenzene Navy blue. 2.6-dichloro-4'-nitro-1,1-azobenzene. 1 (2.) do Z-methylbenzefie Reddish.

Blue-black. (3.) do.. 4! .0h10l' 0b8fl26119 Navy blue. (4.) o.-- Z-methoxybenzene Blue-black. (5.) o 3-nitrobenzene.- Navy blue. (6.) .do..- Z-methyI-S-methoxy- Navy blue.

benzene. (7.) 'do Naphthalene Blue-black.

.2-(2,3-hydroxy'naphthoylemino)- 1' (8.) "-.-.'do L;;;- Naphthalene Blue-black.

Instead "of 4-amino-2,5-di-beta-hydroxyethoxy-Z',6'-dichloro-4'-nitro-1,1-azobenzene other di-hydroxyalkyl ethers of the indicated constitution may be used with the same effect as diazofastnes's properties, particularly of ver'ygoo'd fastness to light. Y r i 35 The water-insoluble disa'zo-dyestufi V W I V of "the iollowingformula:

v I 01 oomomon .W.IOQN QN=N ON=N f 0H e g o1 omomon H I i 00H ooNH' 3 5. Fiber dyed with the water-insoluble disazodyestufls as claimed in claim 1.

dyestufl as claimed in claim 2. r

7. Fiber dyed with the water-insoluble disazodyestufl as claimed in claim 3.

E C! OOHOHOH Cl OGHICHiOH GONE-O01 being a navy-blue powder and yielding, when produced on the fiber. navy-blue dyeings 01 good dyestufi as claimed in claim 4. i'astness properties, particularly of very good fastness to light.

6. Fiber dyed with the water-insoluble disazd- 7 8. Fiber dyed with the water-insoluble disazc- 7 PAUL JijRG- V 

